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Publication numberUS3002003 A
Publication typeGrant
Publication dateSep 26, 1961
Filing dateOct 2, 1959
Priority dateOct 2, 1959
Publication numberUS 3002003 A, US 3002003A, US-A-3002003, US3002003 A, US3002003A
InventorsStewart H Merrill, Cornelius C Unruh
Original AssigneeEastman Kodak Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Azidophthalic anhydrides
US 3002003 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States. Patent" F 3,002,003. I AZIDOPHEHALIC ANHYDRIDES Stewart H. Merrilland Cornelihs C. Unruh, Rochester,

N.Y., assignors-to Eastman Kodak Company, Rochester, N.Y., a corporationof New Jersey No Drawing. Filed'Oct. 2, 19 59, Ser. No. 843,928 3 Claims: (C11 260-3463) of. Bayer and Cantor, Chem. Rev. 54, pageZO (1954), and wil'l be referred to'as-='--N -.i1i the chemi'alf sn ucture's 1: appearing hereinafter;

application is a: conti-riuationsin-part" of ourvco pending application Serial No? 525,368; mod -J29}. 19555 It"-' is k'nown" that certain *aromati'c"azides 'are lfht sensitive and that"physicalmiritures=thereof Withcertain" colloid-materials such as casein; gelatin, methyl 'cellh-" loser synthetic resins;- etc., when -coated" onto a suitable" support material" and exposed" under an appropriateimageuo light, give tanned images-'=whichi are insoluble 30 and ink-receptive; and can function as printing plate" surfaces. For example," a process'ofithis kin diis dscribedbrKalle ace. in British PatentNor 678,599, datedSptember 3; 1952." Such priorartprocesses 'have, however; certain drawbacks: For instance; the "fact that: the'components, ije. the colloid "and'the light-sensitive; compound are separate entities'm'akes'necessarythe taking of special precautions in the preparation" and"processing to ensure uniform distributiorrand proper func tioning of the-components, so that-durable, high quality 40 and reproducible printing surfaces are obtained.

We have now foundthat'soluble, light-sensitive materials can be prepared in which the azido group is attached by chemical bonds to a linear polymer chain. Thus, ,the anew: polymers:perform:*the functions of bbth thee vehicle: and i the sensitizer-i thereby ensuring better control and. reproducibility: Coatings of these poly III'CI'SifIiOIIlJhEif solutions on light exposure to I-a'subje'ct such: as: a 1 line; half-tone or rcont-inuous '-tone iniage;- becomevselectively insolubilized in the exposed areas while the: unexposed' areas 'remain soluble and'iare readily re movable by a suitable solvent thereby=reproduoiiig the said subject or image. Furthermore, mixtures of these polymeric azides andfiother inert .polymerszprovided the selected polymers are compatible with the polymeric azides, when coated anduzexposed under a negative to ultraviolet light, can also form insoluble stencils, It. is I also within the invention to provide. our... new poly: mers with other functional 1 groups .suchlas .carbbXyl .or 1 sulfonic acid groups which? serve to impart improved solubility, in dilute :aqueous alkal-iuand-s ammoniumehy dr'oxide. Thus, exposed -coatingss-camabeemoreereadilyy developed in aqueous -media. The l'various anewpoly? meric. azideswof tour inventionxareparfioulanlytysuitablee fomfor-ming :resist :images :ontprinting plate supportsssnch aseonualurninum; zinc; coppery-magnesium -an'd 'on vari ous-allo'ys thereof? Suchi-resist' images; we have -f6'u'ncl, are dimensionally stable; are ink receptive, andihighlyr suitable for printing surfaces-for lithographicror other printing presses: For further" details? off photographic. processes -whereirr'our new 'polymers'are advantageously 2: employedyreference.mayjberhad -to copending applicam tion Serial No. 525,271, of Stewart H. Melffllzletwalqj filed-;July: 29,w1955, now U.S2=.Patentf:No; 2,9 48,6l0a- It isfiaccordinglyyam objective rof'hour:inventionnto vppoi vide" anew classvofrsoluble light-"sensitive-, film-forminggt organiclpolymers containing; a :substantial proppntionaofis azidougroupsi A- furtherf. objectis :ltGL provider-composig tions of thennew-"polymersegwhichaare "particularly?useftllit for photomechanical reproduction processes. Another object is to providea process for preparing the new class 1 of light-sensitivepolymers.- Other objects will become apparent hereinafter.

In accordance with-sour invention, we prepare lightsensitive filnrfornling azidostyrene homopplyrners containing';the.iollowingrecurringiStructural' 'u'nitz (I) -GHr-CH- wherein the ratio oiiil'tay units to II(b) units in each resin molecule can vary fromr15l9 to 19:1, i.e. 11(b) are present from 5 to mole-percent, and wherein m represents ineach .instance. a digit 1 or 2, n represents.%- a digiffr'om 0to' 2', -,X"represents, achlori-nei-atom', alliyl fgroup 'containingfrom .1 to 4'carbon atoms, age. methyL'T ethyl, propyl; .butyl',- etc., ,an -a1ltoxyfgroup con= tainingffr'om. lto 4 carboniatoms, e.g. meth'oxy, ethoxyj, propoxy, vbutoxy, etc., and a nitro. group, and Krrepreef sents a unitisucli ethylene, ,isobutylene, ,a,11,3'-bi1tadi-. one, styrene an'di substituted styrenes, etc., an aJi-unL-s: saturated; mono or di-carboxylic acid unit suclr; as; acrylic acid; an a-alkylacrylic. acidQ-male'icacid,,citr coniclacidglitacon-icacid;etc. andfthe anhydrides, esters, imides;,N-a1kyl Iimides, ,nitriles, amides, .andjhl V alky1"and.'N,N-dialkyl substituted famide's of 'these acids-;.. funraric and..mesaconic acidsv and theirv alli yl'" esters uitiiles, amides and N-alky1 a11dN,N-dialkylTsubstitutedl amides, vinyl "alkyl ketones suchlas .vinyl methylketone,:, vinylhali'de's such .as vinyl chloride, vinylidene halides; such as vinylide'ne chloride,,and!thevlikeunits,v and' whereinin' each instance inv the above the .alk'yliand. alkoxyj'groups contain from 1 to" 4'carbon. atoms, by; diazotizing'a'p olyaminostyrene oracopolymer of aminostyrene "and reacting the resulting, .diazonium'" salt with} sodium 'azide', followed by separation of the .azidoderiva-e: tiveffomthe "reaction .miziture': While.- the. intermediate aminostyrene polymers can' be prepared/by direct polyg-g meriz a'tiontofthe monomeric aminostyrene alone or with; azcomonomer, wepre'fer: to derive them. fro-muthelcorsi respgndihglj simple styrene polymers It having the. a bovee stmcture',' bi1t-'-without the azido group, by, nitratinguthes styrene nucleus; and then reducing the. nitro derivatives tothe corresponding amine derivative. Where -R -in.-thes abbvestructure IIisflan u, Sunsaturated. di-carboxylics acid'l;unit's',,e.g.,.a 1&1 copolymer of-Ianazidostyreneandu maleie' vacid, the copolymer. can he. treated. 'with acetica anhydride .to; giue the maleic anhydr'ide derivativwand i this can: then bereactediwith'aavarietyzof hydroxyland amino containing components, including hydroxylated azido-containing components which greatly increases the azide content of the polymer molecule, to give the corresponding ester and amide derivatives. In place of the maleic acid-azidostyrene copolymer, there can be employed citraconic or itaconic acid copolymers with the azidostyrene.

To obtain the film-forming, light-sensitive polymers of the invention, wherein the azido grouping is contained in an ester type sidechain of the polymer, as in the azidobenzoates of vinyl alcohol polymers represented, for example, by the homopolymers consisting essentially-of the following recurring structural unit:

(no, -oH,-oH- x (Nah,

or by copolymers consisting essentially of the following recurring structural units in random combination;

(N3) in wherein, the ratio of IV (a) units to IV(b) in each resin molecule can vary fi'om. 1:19 to 19:1, and wherein m, n and X are as previously defined, and R represents a unit such as ethylene, isobutylene, 1,3-butadiene etc., a vinyl or isopropenyl carboxylic ester ether, ketone, carbamate or acetal, and the like units, an o-, mor p-azidobenzyl chloride represented by the general formula:

wherein m, n and X are as above defined, is condensed with a polyvinyl alcohol, a partially hydrolyzed polyvinyl or a poly-isopropenyl ester, e.g. partially hydrolyzed polyvinyl acetate, polyvinyl butyrate, polyvinyl benzoate, polyvinyl carbamate, polyvinyl cinnamate, polyvinyl cyanoacetate, polyvinyl azidobenzoate etc., or with a partially hydrolyzed copolymer of vinyl and isopropenyl esters, or with partial alkyl ethers of polyvinyl alcohol, or with partial polyvinyl acetals. The fi'ee hydroxyl groups in each instance can be partially or substantially completely esterified, as desired, with the azidobenzoyl chloride reactant. Where the esterification of a partially hydrolyzed polyvinyl acetate with azidobenzoyl chloride is incomplete, the final light-sensitive polymer product may contain more than two different units making up the structure such as vinylazidobenzoate units, vinyl acetate units and vinyl alcohol units.

In place of the azidobenzoyl chloride, there may be employed an azidonaphthoyl chloride, azidophenylacyl chlorides such as 0-, mor p-azidophenylacetyl chloride, etc. an azidocinnamoyl chloride, and the like, to give the corresponding polymeric derivatives of the above-mentioned hydroxyl-containing polymers. azido-group-containing acid chlorides are also capable of condensing with other hydroxylic polymeric materials, for example, with naturally occurring materials such as cellulose, starch, guar alginic acid or with their partially esterified or etherified derivatives to give other operable lightsensitive polymers. The said acid chlorides are capable of condensing also with polymeric materials containing amino groups having free hydrogen atoms, for example, with synthetic polymers such as polyvinylamine, polyvinyl anthranilate, polymeric aminotriazoles, etc. as well 'as with naturally occurring polymers such as gelatin to give the corresponding light-sensitive amide derivatives.

' To obtain the film-forming, light-sensitive polymers of The mentioned the invention wherein the azido grouping is contained in I a different ester type of sidechain of-the polymers, as in the azidophthalates of vinyl alcohol polymers represented, for example, by homopolymers consisting essentially of the following recurring structural unit: v -'CH2 'CH COOH . or by copolymers consisting essentially otthe following recurring structural units in random combination: v1) R1- and -onr-on- I] CODE (Nah, v a we wherein the ratio of VI(a) units to VI(b) units in each resin molecule can vary from 1:19 to 19:1, and wherein m, n,X and R are as previously defined, an o-, mor p-azidophthalic anhydride is condensed with a hydroxylic polymer such as mentioned in the process for preparing the light-sensitive polymers of structures III and IV. The

azidophthalic anhydride can be substituted by various azidonaphthalic anhydrides. Also, the azidophthalic and azidonaphthalic anhydrides may be condensed with ami (X). ins-(D),

(Nah,

wherein m, n, X and R are as previously defined, R represents an alkylene group containing from 1 to 4 carbon atoms such as CH --CH CH etc., D represents an atom of oxygen, an atom of sulfur, an imino group or an alkylimino group and p represents a digit 0 or 1, a hydroxylated azido-group-containing compound such as an 0', mor p-azidophenylalkanol such as represented by the general formula:

wherein m, n, X, R D and p are as previously defined, is condensed with a maleic anhydride copolymer, preferably with a 1:1 styrene-maleic anhydride copolymer. As typical azidobenzylalkanols, there may be employed, for example, p-azidobenzyl alcohol, o-azidobenzyl alcohol, m-azidobenzyl alcohol, 2-(azidophenyl)-ethanol, an azidophenoxyethanol, an aliphatic hydroxylated azido compound such as 2-azidoethan01 or Z-aZido-Z-phenylethanol to give the corresponding light-sensitive esters. Also, the maleic anhydride copolymer can be replaced by polyacrylic or polymethacrylic anhydrides to give gen-.

erally similar light-sensitive polymers with the said hydroxylated azido group containing compounds.

To obtain the film-forming, light-sensitive polymers of the invention wherein the azido grouping is contained in our new light-sensitive polymers and the manner of their seems as aeetal group attached to a polymer chain,v as in polyvinyl azidobcnzalacetals consisting essentially of the following, recurring structural unit:

CHO

wherein m, n and X are as previously defined. The inter.-

by the method described by M. O. Forster and H. .M. Judd, J. Chem. Soc. 97, page 254 1910), whereinian aminobenzaldehyde is diazotized and, then treated with" sodium azide to give the corresponding azidobenzaldehyde. Where the poly-vinyl alcohol is only partly acetab. ized, the final light-sensitive polymeric product will'also, contain some unreacted hydroxyl groups and, in theca'se where a polyvinyl ester is employed as the initial polyv meric material and is only partially acetali'zed, thc final light-sensitive polymer may contain both acetal andi'ester groups. It is also within the invention to employpartially hydrolyzed polyvinyl esters and to only partially acet'alize the available hydroxyl groups. The above described lightsensitivepolymeric products containing residual or unreacted hydroxylgroups can advantageously be further 40 modified by acylation with acid chlorides or anhydrides or by carbamylation with isocyanates. For instance, a 7

partial polyvinyl azidobenzalacetal may be acetylated, maleylated, succinoylated, phthaloylated, benzoylated, cinnamoylatcd, etc. t To obtain the light-sensitive polymers of the invention such as polyvinyl azidocarboxylic esters represented, for example, by the recurring structural unit:

ix -CE:--CH-*- wherein R is as previously defined, a polyvinyl halogensubstituted ester such as polyvinyl chloroacetate, polyvinyl u-chloropropionate, polyvinyl o-chlorobutyrate, etc. is reacted with sodium azide to give the said light-sensitive polymer. The light-sensitive resins are substantially composed of units represented by structure IX and accordingly contain a relatively high proportion of azido groups. Various starting copolymers of the said polyvinyl halogenated esters can be employed. However, light-sensitive polymers of the above described kind, we have found, are generally less stable and of a lower order of lightsensitivity than those of structures I-VIH.

. The following examples will serve further to illustrate preparation.

Example 1.---P0'lyazid0styrene 8 cc. of" concentrated hydrochloric acid were added to 20 cc. of a 10% aqueous solution of poly-'p-aminostyrene hydrochloride and the mixture was cooled to 'redissolve on continuedstirring to give a polystyrene-pdiazonium chloride. Anon-filtration, the cooled solution was treated with aqueous sodium azide until'the gas for mation ceased. After standing overnight at room temperatu're, the red precipitate was collected, washed with water, then Washed with methanol and preserved as an alcohol paste which was soluble in dimethylformamide. Analysis of the product showed a nitrogenco'ntent of 25.0% by weight as compared with calculated theory for CgHqNg of 29.0%. This result indicates that the polymer contained approximately 86% by weight of the recurring structural unit:

assuming that all of the nitrogen is contained as azido groups. The above prepared polymeric product was difficult to evaluate sensitornetrically, due to its rather limited solubility. However, a thin coating from .dimethylformamide solution,- when exposed under a negative and developjed' showed unmistakable hardening (insolubilization) mediate azidobenzaldehydes can be prepared, in. general,...25l image areas!" Exompl l is zidostyrene-maleic acid hererap olymcr Aes olution of 20 g. of p-arninostyrene-maleic acid heteropolymer hydrochloride and 60 cc. of. concentrated hydrochloric acid in 250 cc. of water was prepared. This ,ami ;;e:wa8 diazotized at 0-5 C. with 5.2 g. ofsodium nitrite contained in 30 cc. of water.

Afterstirrin'g for one-half hour at 0-10 C., a solution of 5.0g. of sodium azide 'in Water was added. The mixture was allowed to stand several hours, after which the azide product was collected, washed well with water, and dried. The poly-, mer obtainedwas soluble in moist 2-b'utanone, in moist dioxane and indilute aqueous alkali solutions. Analysis of'the polymer product showed that it, contained 14.3%

a by weight of nitrogen as compared to the calculated theory for C H O N of 16.1%. This result indicates the polymer contained approximately 89% by weight of the recurring structural unit:

onr-oH-on-on- 0 0 he in Example 3.-Esterification of partially hydrolyzed poly vinyl acetate with p-azidobenz oyl chloride To a solution of 12.6 g. (0.089 mole of free hydroxyl group) of 47% hydrolyzed, high viscosity polyvinyl acetate in 250 cc. of dry pyridine, there were added 15.0 g. (0.083 mole) of p-azidobenzoyl chloride, and the, mix ture was heated with stirring for 4 hoursatSO" C. .After the solution was diluted with 3 volumes of acetone, the polymer was precipitated in cold water, reprecipitated from acetone, and vacuum dried at room temperature. Analysis of this polymer product showed that it contained 12.7% by Weight of nitrogen as compared with calculated for reaction of 14.2% of nitrogen. This result indicates that the polymer contains predominantly vinyl p-azidobenzoate units:

and some residual vinyl acetate and vinyl alcohol unit s It had a sensitometric speed of 250, but when sensitized by incorporation therewith of a sensitizer, 2-benzoy1- methylene l methyl-B-naphthothiazoline (BNTZ), the speed increased to 1800. The polymer produced excellent resist images.

The p-azidobenzoyl chloride employed in the above example was prepared by diazotizing p-arninobenzoic acid to the corresponding diazonium chloride derivative and reacting this with sodium azide to give p-azidobenzoic acid, which after recrystallization from aqueous methanol, had a melting point of 180182 C. (decomposes). The azidobenzoic acid was then heated for 2 hours at 60-70 C. with 3 parts of. thionyl chloride. Following vacuum evaporation to dryness, the residue was dissolved in a small quantity of hot, dry ligroin. The hot solution was filtered and cooled in ice to crystallize the p-azidobenzoyl chloride, M.P. 57-5 8 C. A sample was dissolved in alkali, then treated with acid to precipitate a substance which was identified as p-azidobenzoic acid. The and rn-azidobenzoyl chlorides can be prepared in similar manner by starting with oand m-aminobenzoic acids.

Example 4.-3-azid0phthalic anhydride 300 g. (1.42 moles) of powdered 3-nitrophthalic acid was added in portions, with stirring, to a solution of 1000 g. (5.3 moles) of anhydrous stannous chloride in 3 liters of concentrated hydrochloric acid while the temperature was maintained at 25-30 C. The hydrochloride of the amino acid soon began to crystallize, and after .being allowed to stand overnight, it was filtered and washed with a little concentrated hydrochloric acid, and vacuum dried. The yield was 217 g. (67% of theory of 3-aminophthalic acid hydrochloride.

. The above amino acid hydrochloride (217 g. or 1.0 mole) was added to a solution of 200 cc. of concentrated hydrochloric acid in 1200 cc. of water. The amine was diazotized at 0-5 C. with 69 g. (1.0 mole) of sodium -.nitrite in 250 cc. of water. Tlhen a solution of 71 g. 1.1 moles) of sodium azide in 250 cc. of water was .added' in small portions while maintaining the tempera :ture below 10 C. Considerable foaming occurred. The azide suspension was mixed well, then allowed to stand in the dark for several hours. The solid was collected, washed with water, and vacuum-dried to yield 165 g. (80% of theory) of 3-azidophthalic acid, M.P. 167- 169 C. (decomposes).

The azidophthalic .acid (0.80 mole) was added to a mixture of 300 cc. of acetic anhydride and 250 ml. benzene, and the slurry was heated at 65-70 for two hours with occasional swirling. The hot solution was then filtered and cooled to crystallize part of the product. The solid was collected and washed with benzene. The filtrate was evaporated by vacuum on the steam bath to recover successive crops of crystals. The combined product was then recrystallized by dissolving it in 350 cc. of boiling anhydrous benzene, followed by the addition of 100 cc. of dry ligroin; After cooling the flask in ice, the product was collected and dried. The yield was 125 g. (83 percent of theory) of 3-azidophthalic anhydride, M.P. l24126 C. (decomposes).

*Exdmple 5.--Esterification of partially hydrolyzed polyvinyl acetate with 3-azid0phthalic anhydride A. To a solution of 10.0 g. of partially hydrolyzed polyvinyl acetate (47% hydrolyzed, molar basis) in swam 'with stirring, for six hours.

of the polymer product showed a nitrogen content of 10.3% by weight as compared with calculated for 100% reaction of 12.8% of nitrogen. This result indicated that the polymer product contained a substantial proper tion of the recurring structural unit:

the remainder of the polymer molecule being made up of vinyl acetate units and some unreacted vinyl alcohol units. The polymer product was dissolved in a dilute aqueous ammonia solution and coated onto a grained aluminum foil. The coated foil was then exposed to a carbon are through a line negative. After development in dilute alkali and inking by the usual method, a clean image corresponding to the negative was obtained when the inked resist image was printed onto paper.

B. To a solution of 295 g. (2.09 moles of free hydroxyl) of 47 molepercent hydrolyzed high viscosity polyvinyl acetate in 5.9 kg. of dry pyridine was added 395 g. (2.09 moles) of 3-azidophthalic anhydride. The solution was heated with stirring for five hours at 50. C., then allowed to stand overnight at room temperature.

After dilution with 1500 cc. of dioxane, the mixture was poured slowly with vigorous stirring into 40 gallons of aqueous 2.5 percent hydrochloric acid. The fine, white, fibrous polymer (600 g.) which precipitated was washed in three changes of fresh water and dried at 40". It was soluble in acetone, dioxane, and dilute aqueous alkali. Analysis of this polymer product showed that it contained 10.8% by weight of nitrogen as compared with calculated for 100% reaction of 12.8% of nitrogen. It had a sensitometric speed through glass of 32.

C. Three and two tenths grams (0.046 mole of free hydroxyl) of 77 mole percent hydrolyzed medium viscosity polyvinyl acetate was soaked for three days in 50 cc. of dry pyridine. This mixture was heated to 50 C. and 9.5 g. (0.050 mole) of 3-azidophthalic anhydride were added. Heating was continued at 50 -60 C., After standing overnight, the solution was poured slowly into one liter of 5 percent aqueous acetic acid with vigorous stirring. A fibrous polymerprecipitated. After reprecipitation from dioxane into water and washing with water, the polymer was vacuum-dried (10 g.). It was soluble in aqueous alkali. Analysis of thispolymer product showed that 7 it contained 16.7% by weight of nitrogen as compared 200 cc. of dry pyridine, there were added 14.2 g. of

3-azidophthalic anhydride prepared as described in Exam- ;ple 4.' The mixture was stirred for 5 hours at 50 -60 C. .and allowed to stand overnight at room temperature. The resulting solution was diluted with 50 cc. of dioxane and poured slowly into 5 liters of 4% aqueous acetic acid. The fibrous polymer product obtained was washed in water and reprecipitatcd from dioxane into water. The dried polymer (l6;-g.) was soluble in dioxane and in dilute aqueous alkali hydroxide solutions. Analysis with calculated for reaction of 16.2% of nitrogen. It had a sensitometric speed through glass of 32.

Accordingly, both of the above procedures B and C gave polymer products consisting predominantly of the recurring structural unit:

CHrCH-- COOH the remainder of the polymer molecule in each instance being residual vinyl acetate and vinyl alcohol units.

Example 6.Esterificati0n of partially hydrolyzed polyvinyl aceiate with 3(4)-azid0phthalic anhydride (mixed isomers) ployed in the above example was prepared in a similar manner as set forth in Example 4 for the preparation of S-azidophthalic anhydride, except that the initial startmg material was phthalic acid which on nitration gave mixed isomeric nitrophthalic acids. The 3(4)-azidophthalio anhydride mixture melted over the range of 75 "-110? C.

B. Ten grams (0.17 mole of free hydroxyl estimated) of 88 percent hydrolyzed high viscosity polyvinyl acetate was heated at 140 in 250 cc. of N,N-dirnethylformamide with stirring until solution occurred. The solution was then cooled to 50 C., and 12.0 g. of acetic anhydride (0.118 mole, calculated to give 53 mole percent total acetate on polymer) was added. The mixture was heated with stirring at 65 C. for two hours, then allowed to stand at room temperature for several hours. A portion d the polymer at this point was precipitated in ether and washed for analysis. It contained 32% by weight oi CH CO-groups as compared with calculated content of 34.5% of CH CO-groups for 53 mole percent of vinyl acetate.

To the remainder of the polymer in solution heated to 45 was added an amount of azidophthalic anhydride' (mixed isomers) equivalent to the free hydroxyl groups,

followed by cc. of pyridine. This mixture was heated with stirring at 45 -55 C. for six hours. After filtra tion and dilution with 100 cc. of dimethylformamide and. 150 cc. of acetone, the polymer was precipitated in 10.

liters of 0.3 percent aqueoushydrochloric acid, washed in fresh water, and dried at 40? C. This polyvinyl acetate azidophthalate was also soluble in'acjet'one and dilute aqueous alkali hydroxide solution. Analysis of this polymer product showed that it contained 10.0% by weight of nitrogen as compared with calculated for 13.0% for 47 mole percent acetate and 47 mole percent azidophthalate. It had a sensitomertic speed through glass of 22. t

C. 2 g. of substantially completely hydrolyzed polyvinyl acetate were dissolved in 100 cc. of hot dimethylformamide. The solution was allowed to cool slowly to about 100 C. and a solution of g. of azidophth'alic anhydride (a mixture of 3- and 4-isomers) in cc. of dimethylformamide was added slowly with stirring. The resulting temperature of the mixture was 80 C. and this material was kept in a stoppered flask for 7 hours in a constant temperature bath at C.

The solution was then poured into 3 liters of distilled water with stirring. The tan, fibrous precipitate was thoroughly washed with distilled water and dried. The nitrogen content of the sample was 10.8% by weight and a sensitometric value of 70 was obtained for a coating of the polymer using dilute ammonium hydroxide solu tion, both as the coating solvent and also as the development solvent to form the resist image.

Example 7.Esterificafi0n of partially hydrolyzed cellulose acetate with 3-azidophthalic anhyd'ride A mixture of 10.1 g. of 3-azidophthalic anhydride and '6- g. of partially hydrolyzed cellulose acetate (24 percent acetyl) in 80 cc. of dry pyridine was stirred at room temperature for 18 hours. This solution was then diluted with 50 cc. of 2-butanone and poured slowly into agitated -methanol. The fibrous polymer was collected, stirred into 200 cc. of dimethylforrnamide in which it formed a gel. This gel was added slowly to 2 liters of 3% aqueous acetic acid and stirred for several hours. The polymm (11 g.) was soluble in dilute aqueous alkali hydroxide solutions. Analysis of this product showed that it contained 11.7% by weight of nitrogen as compared with calculated for 100% reaction of 13.0% of nitrogen. It had a sensitometric speed through glass of 4.

Example 8.Reaction of 3-azid ophtha'lzc anhydride with gelatin To 10 g. of gelatin was dissolved in 110 cc. of water and stirred at 50 C., while 5 g. of 3-azidophthalic anhy= dride was added in small portions along with sufi'ic'ient 10% sodium hydroxide to maintain 'the pH 'at 8-:10. The heating was continued for three hours, after which the solution was acidified with acetic acid to vpH 6. The solution was evaporated to about 80 cc. by exposure to air, and the product (9 g.) was obtained by precipitation in acetone. This gelatin derivative was readily soluble in water. It could be precipitated by the addition of hydrochloric acid, then redissolved in alkali. This poly mer had a sensitometric speed through glass of 4. Y

Example 9.--Esterification of ethylene-vinyl alcohol copolymer with azidophthalic anhydride To a solution of 5.0 g. of ethylene-vinyl alcohol copolymer (containing 66.7 mole percent vinyl alcohol), in 75 cc. of dry pyridine was added an equivalent amount (16.3 g., 0.086 mole) of the mixed isomers of azidophthalic anhyd'ride described in Example 6A. The mixture was heated at C. for four hours and allowed to stand overnight at room temperature. After filtration, the polymer-was precipitated in four liters of one percent agueous'hydrochloric acid, followed by a fresh wash and vacuum'drying at room temperature. The product (14 5 g.)'was soluble in acetone, in dioxane, and in. dilute aqueous alkali hydroxide solution. Analysis of this polymer product showed it to contain 17.2% by weight'of nitrogen 'as compared with calculated for reaction oi l8;8% of nitrogen. Accordingly, it consisted of vinyl 3.- and.4-azidophthalate units, ethylene units and some unreacted vinyl alcohol units. It had a sensitometric speedthrough glass of 16.

Example 10.Esterificati0n of styrene-maleic anhydrid heteropolymer with fl-(4-azidophenoxy)ethanol To a solution of 13.0 g. (0.064 mole) of styrenemaleic anhydride heteropolyrner in cc. of dry pyridine at 70 C. was added 10.0 g. (0.056 mole) of ti- (4-azidophenoxy)ethanol. The mixture was maintained at 70 for four hours and allowed to stand over night at room temperature. After dilution with 50 cc. of acetone, the polymer was precipitated in two liters of ethyl ether, then reprecipitated from 250 cc. of acetone into three liters of 0.3 percent hydrochloric acid. After washing in water the product (12 g.) was dried at 40 C. It was soluble in dilute aqueous ammonia containing a small amount of ethanol. Analysis of this polymer product showed that it contained 7.5% by weight of nitrogen 'as compared with calculated for 100% reaction of 10.2% nitrogen. This result indicates that the polymer was made up of a substantial proportion of the recurring structural unit:

dn h-onn-0-Om the remainder of the polymer molecule being non esterig,

once "of platinum oxide. The ,B-(4-aminophenoxy ethf anol (15.0 g., 0.098 mole) was dissolved in a solution 30 cc. of concentrated hydrochloric acid in cc. of water. The amine was diazotized at 0-5 C. with 7.0 g. (0.10 mole) of sodium nitrite in 30 cc. of water. Then a solutionzof 7 5"v g. (0.11 mole) of sodium az'ido in 30 cc. of water was added in portions while keeping the temperature below 10 C. .The evolution of nitrogen caused considerable foaming. The precipitate which formed was allowed to stand for several hours at room temperature, then it was collected, washed with water, and vacuum dried. The yield of p-(4-azidophenoxy)ethanol, M.P. 37-38", was 15 g. (85 percent). Analysis gave 22.7% by weight of nitrogen as compared with calculated for CaHgOgNs of 23.5% of nitrogen.

Example 11.-Esterification of styrene-maleic anhydride heteropolymer with m-azidobenzyl alcohol Four grams (0.027 mole) of m-azidobenzyl alcohol was dissolved in a solution of 8.1 g. (0.040 mole) of styrene-maleic anhydride heteropolymer in 90 cc. of dry pyridine and heated at 65 for seven hours, and after standing overnight the product was isolated and purified similarly to Example 10. The polymer was soluble in dilute aqueous ammonia. Analysis showed it to contain 5.7% by weight of nitrogen as compared with calculated for 100% reaction of 9.3% of nitrogen. This result indicates that the polymer product was made up of a substantial proportion of the recurring structural unit:

lo ('10 a... N:

the remainder of the polymer molecule being nonesterilied units. The polymer had a sensitometric speed through glass of 16. i The m-azidobenzyl alcohol employed in the above example was prepared as follows: m-nitrobenzyl alcohol was hydrogenated to the amine. The latter was then converted to the diazonium salt, followed by displacement with sodium azide to yield an oil which was taken 'up in ether and dried. Evaporation of the ether solution left a residue which on distillation at 92 C., at a pressure of 9 mm., yielded m-azidobenzyl alcohol which analyzed 28.6% by weight of nitrogen as compared with calculated for C H N of 28.2% of nitrogen.

Example 12.P0lyvinyl azidoacetate A. To a solution of 5 g. of polyvinyl chloroacetate in 35 cc. of acetone, there were added 15 cc. of dioxane, 5 cc. of water and 4 g. of sodium azide. This mixture "was heated at reflux for 3 hours. The solution was decanted from the solid salt and concentrated to one-half volume. The polymer was then precipitated in water and dried. A coating on a piece of a paper lithographic printing plate, which has a casein surface, was exposed to light under a negative and developed in acetone. An image was formed, but the speed was relatively low.

' B. To a solution of 5.0 g'. of polyvinyl chloroacetate in 50 cc. of dioxane was added a solution of 3.0 g. of sodium azide in cc. of water, followed by 30 cc. of ethanol. The mixture was refluxed for min. and 10 cc. of water were added. After an additional 30 min. period of refluxing, the upper liquid phase was decanted off and water was added to the heavier phase to coagulate the product. The soft polymer obtained was washed with water and reprecipitated from acetone into water, followed by an alcohol wash and an ether wash. The analysis of the dried polymer product showed that it contained 30.6% by weight of nitrogen and less than 1% by weight of chlorine as compared with calculated for C H O N of 33.0% of nitrogen. On coating from acetone, exposure of the coating under a negative and development in acetone, at resist image was formed.

Example l3.-m-Azidobenzaldehyde polyvinyl acetal To a solution of 5.9 g. of polyvinyl acetate in 30 cc. of dioxane, there were added 13.5 g. of m-azidobenzaldehyde followed by a dropwise additon of 0.5 g. of sulfuric acid. The solution was heated in a 40 C. bath for 24 hours. The catalyst was neutralized with 1 g. of sodium acetate and the product was precipitated in water. Reprecipitation in ether from acetone yielded a rubberlike polymer. It contained about 1% by weight of nitrogen as compared with calculated for reaction of 19.3% of nitrogen. It had a sensitiometric speed of 1.6.

The m-azidobenzaldehyde employed in the above example was prepared as follows: A solution of 24 g. of m-aminobenzaldehyde and 60 cc. of concentrated hydro chloric acid in 250 cc. of water was diazotized and treated with sodium azide in the usual manner. The oil that separated was taken up in ether. After a water wash and a sodium carbonate wash, the ether solution was dried and evaporated. The product distilled at 65 -70 C. at a'pressure of 0.5 mm. giving a pale green liquid. Analysis showed that it contained 27.8% by weight of nitrogen as compared with calculated for C H ON of 28.7% of nitrogen. Example 14.--4-azidophthalic acid and anhydride thereof In a solution of 8.5 g. (0.21 mole) of sodium hydroxide in 75 ml. of water was dissolved 21 g. (0.1 mole) of 4-nitrophthalic acid. The pH was adjusted to 8-9 with dilute acetic acid. Reduction on the Parr hydrogenation apparatus with 0.1 g. of platinum oxide at 3 atmospheres hydrogen pressure required 4 hours at about 45 C. The catalyst was removed by filtration and 50 ml. of concen trated hydrochloric acid was added with cooling. Diazotization was accomplished by adding a 25 percent solution of sodium nitrite in increments at 05 C. The diazonium salt was converted to the azide with an excess of 20 percent sodium azide. On chilling 18 g. of 4-azidophthalic acid crystallized. After two recrystallizations from water, the melting point of a sample was -171 C. (dec.).

Analysis, percent by weight.-Calc. for C H O N C, 46.3; H, 2.4; N, 20.3. Found: C, 46.8; H, 3.0; N, 20.6.

The 18 g. of 4-azidophthalie acid was heated at reflux with 15 ml. of acetic anhydride and 15 ml. of benzene until solution occurred. After filtration, nearly all of the solvents were removed by vacuum evaporation with gentle warming. To the residue was added 50 ml. of carbon tetrachloride, and the mixture was chilled to crystallize the product (15 g.), 4-azidophthalic anhydride having a melting point of 88-89 C.

While the azidophthalic anhydrides of the invention have functioned in the above examples as intermediates to form light-sensitive polymers by condensation thereof with hydroxyl-containing polymers, the described 3- and 4-azidophthalic anhydrides per se and their mixtures are also light-sensitive and capable of reproducing subjects and images. They are particularly useful when used in vesicular films. The following example illustrates this utility. Example 15 Thirty parts of Saran F220 (a commercial vinylidene chloride-acrylom'trile copolymer) are dissolved by turnbling over night with 70 parts of methylethyl ketoue. To this solution are added three parts of 4-azidophthalic anhydride dissolved in 15 parts of methyl ethyl ketone. After mixing and filtering, the resulting solution is coated on glass, Mylar, or other suitable support to a dry thickness of 0.0005". The coating is cured 15 minutes at 70 C. and 15 minutes at 100 C. After exposure through a step density tablet (0.3 density increments) to the light of a mercury vapor lamp, the image is developed by immersing in an air oven for 30 seconds at 90 C. Three to five steps of the tablet are visible in the resulting image which consists of uniform small bubbles of the order of 1 micron in diameter. The image may be made permanent by re-exposing to the direct rays of the mercury lamp and afterward maintaining the film at room temperature to permit the nitrogen evolved to dilfuse out 13 of the layer. If a line copy negative is used, a clean, sharp print of excellent resolution is obtained. With continuous tone images the contrast is rather high unless the subject is one of low brightness range. The proportions mentioned above are by weight.

In place of the 4-azidophthalic anhydride in the above example, there may be substituted a like amount of 3- azidophthalic anhydride to give a generally similar result.

By proceeding as set forth in the above examples, other light-sensitive materials having generally similar properties can likewise be prepared. Thus, any of the mentioned intermediate natural and synthetic polymers and mentioned intermediate monomeric compounds containing one or more azido groups and containing another functional group by means of which they may be attached to the polymer molecules. Where an azidophthalic anhydride is employed as the intermediate, it has the further advantage of generating a carboxyl group on reaction with hydroxylic polymers so that alkali solubility results. This is of considerable advantage since aqueous solutions can be used for processing. The azidostyrenemaleic acid heteropolymers are likewise alkali-soluble. However, those of our light-sensitive polymers which are insoluble in water, but soluble in organic solvents can be processed readily with certain solvents such as acetone, methyl ethyl ketone, dimethylformamide, and the like.

What we claim is:

1. An azidophthalic anhydride of the formula:

2. 3-azidophtha1ic anhydride. 3. 4-azidophthalic anhydride.

References Cited in the file of this patent Karrer: Organic Chemistry (Elsevier (1938)), p. 487.

Non-Patent Citations
Reference
1 *None
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3140299 *Apr 27, 1962Jul 7, 1964Gen ElectricDerivatives of trimellitic acid anhydrides
US3211752 *Feb 12, 1962Oct 12, 1965Hercules Powder Co LtdCross-linking polymers
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US3345171 *Dec 2, 1963Oct 3, 1967Gevaert Photo Prod NvPhotochemical insolubilization of polymers
US3467630 *Jul 29, 1966Sep 16, 1969Agfa Gevaert AgMethod of producing light-sensitive photocrosslinkable polymers
US3884703 *Apr 11, 1973May 20, 1975Hitachi LtdBisazide sensitized photoresistor composition with diacetone acrylamide
US4023973 *Apr 17, 1975May 17, 1977Japan Synthetic Rubber Co., Ltd.Photosensitive composition using maleic anhydride adduct of a 1,2 polybutadiene
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US5585225 *Oct 27, 1994Dec 17, 1996Exxon Chemical Patents Inc.UV/EB curable butyl copolymers for lithographic and corrosion-resistant coating applications
US5585416 *Jun 7, 1995Dec 17, 1996Exxon Chemical Patents Inc.UV/EB curable butyl copolymers for lithographic and corrosion-resistant coating applications
US5587261 *Jun 7, 1995Dec 24, 1996Exxon Chemical Patents Inc.UV/EB curable butyl copolymers for lithographic and corrosion-resistant coating
US5591551 *Jun 7, 1995Jan 7, 1997Exxon Chemical Patents Inc.UV/EB curable butyl copolymers for lithographic and corrosion-resistant coating applications
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EP0002439A2 *Oct 6, 1978Jun 27, 1979Ciba-Geigy AgPolymers susceptible to crosslinking on exposure to light with azidophthalimidyl-moieties, process for their preparation and their photochemical application
EP0002439A3 *Oct 6, 1978Jul 11, 1979Ciba-Geigy AgPolymers susceptible to crosslinking on exposure to light with azidophthalimidyl-moieties, process for their preparation and their photochemical application
EP2348116A2May 12, 2004Jul 27, 2011The University Of QueenslandA method of increasing the total or soluble carbohydrate content or sweetness of an endogenous carbohydrate by catalysing the conversion of an endogenous sugar to an alien sugar
Classifications
U.S. Classification549/243, 526/310, 534/564, 534/558, 536/32, 430/300, 430/195, 536/3, 528/228
International ClassificationC07D307/89, C08K5/28, C08F2/50, C08F8/30, G03C5/60
Cooperative ClassificationC08F8/30, C08K5/28, C07C247/00
European ClassificationC07C247/00, C08K5/28, C08F8/30